Biochar plays a significant role in soil remediation. However, the simultaneous immobilization mechanism and relationship of biochar to cations and anions have never been clear. We designed a batch incubation experiment to investigate the impact of corncob-based biochars to cadmium (Cd) and arsenic (As) contaminations in yellow soil and cinnamon soil, and analyze the relationships among biochars physicochemical characteristics (surface area: SA, total pore volume: TV, average pore size: AV and the C/O rate), soil properties, metals immobilization and microbial diversity indices. Results showed that the modified biochars (inorganic-modified biochar: BCTD) had a good effect on heavy metals immobilization and transformed acid extractable and reducible fraction into the residual fraction. Total nitrogen, organic matter and available potassium increased in both soils after biochar application. The principal component analysis presented that the smaller C/O rate was favorable to As stabilization; the SA and TV of biochar were negatively correlated with the leaching concentration of Cd. The larger surface area, higher porosity and organic matters of biochar were more beneficial to soil microbial diversity. This work not only can demonstrate remediation mechanisms of heavy metals contaminated soil by biochars, but also gain an application of biochars technology in the recycling and reutilize of agricultural waste, and provide a clear strategy for heavy metals contaminated soil, especially As and Cd.